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DOI: https://doi.org/10.6023/A26070272

可见光诱导的单电子和能量转移协同促进环酮肟酯的开环/氮杂芳基化反应

  • 赵瑜 ,
  • 邢彤彤 ,
  • 魏思文 ,
  • 白育斌 ,
  • 李金凤 ,
  • 丁卫
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  • a延安大学 化学与化工学院 陕西省化学反应工程重点实验室 陕西 延安 716000;
    b郑州大学 河南先进技术研究院 河南 郑州 450001

收稿日期: 2026-07-29

  网络出版日期: 2026-09-01

基金资助

国家自然科学基金(No. 22161047)和陕西省重点研发计划一般项目（No. 2025NC-YBXM-242）资助.

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Photoinduced Ring-opening/ Azaarylation of Cyclic Oxime Esters via Single Electron and Energy Transfer Synergistic Catalysis

  • Yu Zhao ,
  • Tongtong Xing ,
  • Siwen Wei ,
  • Yubin Bai ,
  • Jinfeng Li ,
  • Wei Ding
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  • aCollege of Chemistry and Chemical Engineering, Shaanxi Key Laboratory of Chemical Reaction Engineering, Yan’an University, Yan’an 716000, Shaanxi Province, China;
    bHenan Institute of Advanced Technology, Zhengzhou University, Zhengzhou 450001, Henan Province, China

Received date: 2026-07-29

  Online published: 2026-09-01

Supported by

National Natural Science Foundation of China (No. 22161047) and Key Research and Development Program of Shaanxi（No. 2025NC-YBXM-242）.

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摘要

含氮杂环化合物广泛存在于天然产物、医药、农药、染料以及材料科学等研究领域。例如,1,1-二芳基结构是农药中重要的结构模块。开发了一种可见光诱导环酮肟酯的开环/ 氮杂芳基化反应的方法。该反应是以二异丙基乙胺为还原剂,氮杂芳基腈化合物为氮杂芳基源,在光催化剂的存在下和蓝光的照射下,通过单电子还原和能量转移的协同催化,进而促进自由基-自由基交叉偶联的反应。该策略在温和的反应条件下,具有良好的官能团兼容性和宽广的底物范围,以及操作简单的特点,并以中等到优异的产率,直接制备了一系列氮杂芳基取代的烷基腈类化合物,包括1,1-二芳基结构的烷基腈化合物。最后,通过一系列机理实验提出了协同催化的反应机理途径。

关键词： 可见光诱导的协同催化; 环酮肟酯; 氮杂芳基化; 氮杂芳基取代的烷基腈化合物

本文引用格式

赵瑜 , 邢彤彤 , 魏思文 , 白育斌 , 李金凤 , 丁卫 . 可见光诱导的单电子和能量转移协同促进环酮肟酯的开环/氮杂芳基化反应[J]. 化学学报, 0 : 26070272 -26070272 . DOI: 10.6023/A26070272

Abstract

Nitrogen-containing heterocyclic compounds widely exist in natural products, pharmaceuticals, dyes and materials science. For example, 1, 1-diaryl skeleton is an important structural unit in pesticides. The cyano group is a multifunctional group in organic synthesis. So, Development of a green and efficient method for the synthesis of alkyl nitriles containing azaaryl structures is of great research significance. Herein, a photoinduced ring-opening/ azaarylation of cyclic oxime esters is described. This reaction utilized 2.2 equiv of diisopropylethylamine (DIPEA) as reductant, 1.5 equiv of azaaryl nitriles as azaaryl sources, 1 mol% amount of [Ir(dF(CF3)ppy)2dtbbpy]PF6 as photocatalyst, under the blue irradiation for 7 hours, and proceeded well via a radical-radical cross coupling mediated by single electron transfer (SET) and energy transfer (EnT) synergistic catalysis. This strategy features well functional group tolerance, broad substrate scope, simple experimental operation, for the facile synthesis of a series of azaaryl substituted aliphatic nitriles in moderate to excellent yields under the mild reaction conditions. At the same time, for the further synthetic application, the gram-scale and sun-irradiated photochemical reaction of model reaction were performed, both obtaining the target product in good yield. In the standard reaction condition, while 1.2 equiv of DIPEA was used, the target product was obtained in 73% isolated yield. So, in order to gain more insight into this reaction, a series of mechanistic experiments were performed. Meanwhile, radical trapping experiment of TEMPO displayed the involvement of radical intermediate in model reaction; fluorescence quenching analysis of Ir photocatalyst and some control experiments explained photoinduced single electron reduction of azaaryl nitriles using DIPEA as reductant; UV-vis spectra experiments, photosensitized reaction of cyclic oxime esters , addition of PhSeSePh and 1, 1-diaryl ethylene to cyclic oxime esters, confirmed photosensitized pathway of cyclic oxime esters with Ir photocatalyst; the light on/ off experiments declared that this reaction is a photoinduced synthetic reaction. And then a plausible mechanism of photoinduced synergistic catalysis is proposed.

Key words： photoinduced synergistic catalysis; cyclic oxime esters; azaarylation; azaaryl substituted aliphatic nitriles

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